5, 5, 5-trichloropentyl phenyl ethers



Patented Nov. 29, 1949 unis-Tao suresmm ounce:

214-891935 5t5,5-IRIGHLOR;OPENTYL PHENYL ETHERS Norman E; SearleWilmington; Dela. assign-or? to.

E; I: dnPont' de-Nemours &;Gompany, Wilmingi ton; Helga corporation ofDelaware No Drawing. Application" A ugus't 16} 1936i Serial N0. 691,1363

This invention relates to 5,55-trichloropentyl* phenyl ethers and toinsecticidal compositions and methodsemployingthe compounds. as anactive toxica'nt.

The compoundsoijtheinvention may be're'pre sented by the formula.

O-xacnolcca wherein X is a chalcogen" of atomic weight lessthanthirty-thre'e (33). Compounds represented by this formula are theether, 5,5,5-trichloropentyl phenyl'oxide or5,5,5 trichloropentyl.phenylether as" it will be called. hereinafter; and" the corresponding thio'l'ether; 515,5-trichlropentyl phenyl It is aniob'jecti of the inventionto: provide new" compounds, and more particularlyome'ga-trichloropent'yl" plienyl eth'ers: It' is" a. further object toprovideinsecticidal compositions which are effective and economical touse. Anotherob ject is. to provide methods for the controlof insects;Still further object'swillbe'c'ome apparent hereinafter.

The foregoing'othe'r objects of the invention are attained by means of'5,5,5-trichlorop'entyl: plienyl others and byinsecticidalcompositionsand methods employing these compounds as active toxicants': for thecontrol of insect pests.

The 5,5,5-trichloropent yl pheny-l ethers of this invention may'beprepared by the reaction, preferably in an alkaline medium and a solventof the polar type such-asalcohol; acetoneand the like, of. a5,-5,5-trichloropentyl v halide with: aphenol of the formula where X isr a chalcogen as defined: above:

The compounds. of. the: invention, which. are usually, colorless oil,vhave: definite insecticidal nropertiesrand may be employed as the activetoxicants in -insecticidal spray and dustlcompositions. In suchcompositions. 5,5,5-trichloropentyl phenyl ethers may be admixed withappropriate insecticidal? a-d3'uv-a-nt's to provide composinon-sin the:form of solutionsina suitable solvent,

dust compositions; or: slur-ries or emulsions in waten.

Where a. solution of the compounds of this invention in a solvent isdesired, such as for use in fly spray compositions, the adjuvant may bea hydrocarbon solvent and is preferably a refined kerosene of the typeknown in the art as a fly spray base solvent. Other solvents, such astritai nin'g 'dn'e -ofthe adjuvants commontotlc'e dust c'onipos'itibns-describ'ed above;- said poWder then-b'eing dispersed for actual usage26 in theawater usually with the-aid or an adiu'vant such: as a wetting;dispersing; or emulsifying" agent. Typical of tlie adjuvants of thistyp'e are' materials such as tne sulfated liigher alcohols,polyvinylal'col'io'lsg polyethylene 'oxides; the alkali metali' oramine? salts-or oleic acid, the sultonated; animal? andive'getableoil's, such as sulfonated fish a-n'di ca'storf oil s; the Y sulfonatedpetroleum- I oil s, alkali metal salts of: allky-l naphthalenesulfonicacids, and such proprietary preparations asare" 30 listed indetail in BulIetin EP-GO'I of the Bureau of Entomology and PlantQuarantine of the U. S. Dept/.- 4 of Agricultilrea If theinseotioidahcoinliosition-is desired in the former a=liquid to-beu's'ed' as-a'dispersion or emul si'on in water, then it is "preferred"to prepare a relatively concentrated composition of the active agentdissolved in a suitable solvent selected ac:

prepare} anemulsio'n 'of' the active agent in" a" lm nomsolvent in--certainc'ases wliere such te'ch nique ism'oreapplicahle; said solutionor emulsion subsequently being dispersed: in water to permit Suitableapplication; In Substantially" all compositions prepared for ultimate"use as emul- 451- sionsin'wate'r'; theessentialiadjuvantis a1.wetting,.

dispersing, or? emulsifying'ag'ent such as" have Thef compoundso'ftliemention may also be: incorporated" in' other standard'- insecticidal"and. fungicidal compositions"eitlfef'as thesole toxic" ingredient or incombination with other parasitical toxicants, such as -b S phenyl) 1,1,1-trichloroethane, rotenone, py-

rethrum, cryolite, organic thiocyanates, oils, sul- 5 5 fur, arsenates,and copper compounds,

This example illustrates a suitable method for the preparation of5,5,5-trichloropenty1 phenyl ether.

A solution of sodium butylate prepared by dissolving 4.6 parts by weightof sodium in 120 parts by weight of dry butanol is added to a mixture of42 parts by'weight of 1,1,1,5-tetrachloropentane and 18.8 parts byweight of phenol and refluxed with stirring for 2 hours. The reactionmixture is poured into water, the oil separated with ether, and theether layer extracted with 2 per cent sodium hydroxide followed byextraction with water until neutral. After drying over sodium sulfate,the product is vacuum distilled, yielding 34 parts by weight (64 percent) of colorless oil boiling at 130-3/3 mm. This product contains byanalysis 38.37 per cent chlorine.

Example 2 This example illustrates a suitable method for the preparationof 5,5,5-trichloropentyl phenyl sulfide.

A mixture comprising 4 parts by weight of sodium hydroxide, 100 parts byweight of methanol, 11 parts by weight of thiophenol, and 30.2 parts byweight of 5,5,5-trichloropentyl iodide is refluxed with stirring for 4hours. The reaction mixture is then poured into water, the oil separatedwith ether and the ether layer extracted with 2 per cent aqueous sodiumhydroxide solution followed by extraction with water until neutral.After drying over sodium sulfate, the product is vacuum distilled,yielding 21 parts by weight (71 per cent) of colorless oil distilling at164-6/3 mm. This product contains by analysis 11.39 per cent sulfur ascompared with the calculated value of 11.29 per cent.

Example 3 A solution of 1 part by weight of 5,5,5-trichloropentyl phenylether prepared according to the process of Example 1 in 79 parts byweight of acetone is thoroly mixed with 99 parts by weight of talc toform a paste. Upon evaporation of the acetone with good agitation, ahomogeneous dust results which is suitable for dusting foliage tocontrol effectively a wide variety of insects.

An effective insecticidal dust may be prepared similarly, of course, byusing the thioether prepared according to the process of Example 2instead of the 5,5,5-trichlorophentyl phenyl ether used in this example.

The proportions of this example may be varied to give dust compositionscontaining greater or lesser amounts of the active ingredient or the 1per cent dust thus obtained may be diluted with talc simply bymechanical mixture therewith to provide a more dilute dust.

Example 4 Ten (10) parts by weight of the product of Example 2 and 1part by weight of technical n-dodecyl alcohol is thoroughly mixed with44.5 parts by weight of ground fullers earth having an average particlesize of about 40 microns. This mixture is then blended with 44.5 partsby weight of finely powdered tale to give a homogeneous powder. Thepowder is dispersible with water for application to foliage as a sprayfor the control of insect pests, such as Mexican bean beetle, redspider; and other insect pests.

The product of Example 1 may be used similarly instead of the thioetherof this example to give satisfactory water dispersible powders.

The proportions of this example may be varied to give a lessconcentrated product, though in compositions of this type as high aconcentration as possible is desirable consistent with a dry,free-flowing powder.

Example 5 The 5,5,5-trichloropentyl phenyl ether of Example 1 isdissolved in acetone to a concentration of 2.5 per cent by weighttogether with 0.25 per cent by weight of a wetting agent, the activeagent of which is the sodium salt of sulfated oleyl acetate. Thiscomposition is suitable for dispersing in water to provide a contactinsecticidal spray for the control of insect pests such as aphid.

5,5,5-trichloropentyl phenyl sulfide as prepared according to theteachings of Example 2 may be used satisfactorily in place of5,5,5-trichloropentyl phenyl ether to prepare suitable compositionsaccording to the teachings of this example.

The proportions may be varied to provide greater or less concentrationof the active ingredient and other solvents or other wetting agents maybe employed.

I claim:

. 1. A compound represented by the formula wherein X is a chalcogen ofatomic weight less than thirty three (33).

v 2. 5,5,5-trichloropentyl phenyl ether.

3. 5,5,5-trichloropentyl phenyl sulfide.

. NORMAN E. SEARLE.

REFERENCES CITED 7 The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,819,132 Spengler Aug. 8, 19312,108,606 Muller et a] Feb. 15, 1938 2,303,683 Coleman Dec. 1, 19422,329,074 Muller Sept. 7, 1943 2,425,426 Joyce Aug. 12, 1947 OTHERREFERENCES Bennet et al., J. Chem. Society (London) 1929, pp. 2567-2572,Abstracted in 24 Chem. Abst; 13396. Gaubert et al., J. Chem. Society(London) 1937, pp. 1974-1979, abstracted in 32 Chem. Abst. 16533.

